Pathogen-resistant fabrics

ABSTRACT

A pathogen-resistant fabric comprising one or more photocatalysts capable of generating singlet oxygen from ambient air. The pathogen-resistant fabric may optionally include one or more singlet oxygen traps.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a Divisional of U.S. Utility application having Ser.No. 11/894,374, filed on Aug. 20, 2007, which claimed the benefit ofU.S. Provisional Application having Ser. No. 60/950,323 filed Jul. 17,2007, and further claims priority from U.S. Utility application havingSer. No. 10/931,121 filed Aug. 30, 2004 (now U.S. Pat. No. 7,259,122),which claimed the benefit of U.S. Provisional Application having Ser.No. 60/498,980, filed Aug. 29, 2003.

GOVERNMENT LICENSE RIGHTS

The U.S. Government has a paid-up license in this invention and theright in limited circumstances to require the patent owner to licenseothers on reasonable terms as provided by the terms of “Lightweight andLow Cost Flexible Structure Textiles” U.S. Army Phase I Small BusinessInnovation Research Grant Contract No. DAAD16-03-C-0011.

FIELD OF THE INVENTION

The invention relates to pathogen-resistant fabrics.

BACKGROUND OF THE INVENTION

Exposure to pathogens, such as and without limitation toxic chemical andbiological agents, is a growing concern to both military and civilianorganizations alike. Areas of enhanced vulnerability include assembliesof persons, whether military or civilian. One such scenario includesmilitary personnel assembled within one or more tents and/or portableshelters.

In order to mitigate the harmful effects of an exposure to pathogens,many military shelters are constructed from fabrics which include one ormore polymeric materials exhibiting barrier properties to one or moretoxic agents. Many of these fabrics comprise, for example,fluoropolymers such a polytetrafluoroethylene (“PTFE”). One suchcomposite material comprises Teflon coated Kevlar. While such compositesdemonstrate acceptable barrier properties, these barrier shelter fabricsare expensive and require multiple manufacturing operations to joinvarious fabric segments. The high costs of materials in combination withhigh manufacturing costs limit the availability of such prior artfabrics for widespread use.

As a result, most real-world military shelters are not made from suchfabrics. Rather, current shelters are formed using materials havinginferior resistance. For example, forces of the United States of Americatypically utilize a General Purpose Shelter Fabric (“GP Fabric”)manufactured from cloth coated with polyvinyl chloride (“PVC”). GPFabric is relatively inexpensive and affords soldiers adequateprotection against inclement weather including rain, snow, wind, anddust storms. Shelters made from GP Fabric, however, offer minimalprotection. Such prior art shelters require an additional M28 Saranexliner to impart acceptable barrier properties. As those skilled in theart will appreciate, use of such liners adds to the overall weight,cost, and complexity, of the shelter.

SUMMARY OF THE INVENTION

A pathogen-resistant fabric is presented. The pathogen-resistant fabriccomprises a plurality of polyurethane polymer chains, a phthalocyaninephotocatalyst, a singlet oxygen trap molecule, wherein that singletoxygen trap reacts with singlet oxygen produced by the photocatalyst.

In certain embodiments, Applicant's pathogen-resistant fabrics are usedin personal protective equipment. In certain embodiments, such personalprotective equipment comprises clothing, such as and without limitationshirts, pants, gloves, socks, boots, helmets, and the like. In otherembodiments, such personal protective equipment comprises the interior,exterior, or both, of portable shelters. Applicant's method usesconventional coating methods, such as knife coating, spray coating,calendaring, and the like. Waterborne coatings are desirable because ofinherent low toxicity and low flammability properties. Applicant'scoating solutions rapidly and uniformly spread over substrate surfaces,including the seams, thereby producing a continuous barrier afterdrying. Applicant's coating effectively “hardens” the personalprotective equipment, i.e. enhances its barrier properties with respectto pathogens.

In certain embodiments, Applicant's invention can be used to form afabric which includes a photocatalyst capable of producing singletoxygen. In certain embodiments, Applicant's fabric includes a singletoxygen scavenger.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a cross-sectional view showing Applicant's pathogen-resistantcoating disposed on one surface of a first embodiment of Applicant'ssubstrate;

FIG. 1B is a cross-sectional view showing a second embodiment ofApplicant's substrate;

FIG. 1C is a cross-sectional view showing a third embodiment ofApplicant's substrate;

FIG. 2 is a block diagram showing Applicant's pathogen-resistant coatingdisposed on two surfaces of a substrate;

FIG. 3A is a block diagram showing a polymer chain comprising aplurality of photocatalyst moieties, and a plurality of singlet oxygentrap moieties, chemically bonded thereto;

FIG. 3B is a block diagram showing Applicant's pathogen-resistantcoating comprising a plurality of the polymers of FIG. 3A;

FIG. 4 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 3B disposed on one surface of asubstrate;

FIG. 5 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 3B disposed on a first surface of asubstrate, and a second embodiment of the pathogen-resistant coating ofFIG. 3B disposed on a second surface of the substrate;

FIG. 6A is a block diagram showing a polymer chain comprising aplurality of photocatalyst moieties chemically bonded thereto, wherein asinglet oxygen trap is chemically attached to each photocatalyst moiety;

FIG. 6B is a block diagram showing Applicant's pathogen-resistantcoating comprising a plurality of the polymers of FIG. 6A;

FIG. 7 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 6B disposed on one surface of asubstrate;

FIG. 8 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 6B disposed on a first surface of asubstrate, and a second embodiment of the pathogen-resistant coating ofFIG. 6B disposed on a second surface of the substrate;

FIG. 9A is a block diagram showing a polymer chain comprising aplurality of photocatalyst moieties chemically bonded thereto, whereintwo singlet oxygen traps are chemically attached to each photocatalystmoiety;

FIG. 9B is a block diagram showing Applicant's pathogen-resistantcoating comprising a plurality of the polymers of FIG. 9A;

FIG. 10 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 9B disposed on one surface of asubstrate;

FIG. 11 is a block diagram showing a first embodiment of thepathogen-resistant coating of FIG. 9B disposed on a first surface of asubstrate, and a second embodiment of the pathogen-resistant coating ofFIG. 9B disposed on a second surface of the substrate;

FIG. 12A summarizes the steps of a reaction scheme to form adi-pyridone, di-cyanuric chloride substituted porphyrin;

FIG. 12B summarizes the steps of a reaction scheme to form a polymercomprising a pendent di-pyridone substituted porphyrin;

FIG. 13A summarizes the steps of a reaction scheme to form adi-pyridone, di-cyanuric chloride substituted phthalocyanine;

FIG. 13B summarizes the steps of a reaction scheme to form a polymercomprising a pendent di-pyridone substituted phthalocyanine;

FIG. 14 summarizes the steps of a reaction scheme to form atetra-pyridone substituted phthalocyanine;

FIG. 15A summarizes the steps of a reaction scheme to form atetra-cyanuric chloride substituted phthalocyanine;

FIG. 15B summarizes the steps of a reaction scheme to form a polymercomprising a pendent substituted phthalocyanine;

FIG. 16A summarizes the steps of a reaction scheme to form a tetra-bromosubstituted porphyrin;

FIG. 16B shows the reaction of a tetra-bromo-substituted porphyrin witha pyridone anion to form a tetra-pyridone substituted porphyrin;

FIG. 17 summarizes the steps of a reaction scheme to form a polymercomprising a pendent substituted photocatalyst, wherein thephotocatalyst is selected from the group consisting of a phthalocyanineand a porphyrin;

FIG. 18 summarizes the steps of a reaction scheme to form a polymercomprising a pendent substituted photocatalyst in combination with twosinglet oxygen traps, wherein the photocatalyst is selected from thegroup consisting of a phthalocyanine and a porphyrin.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention is described in preferred embodiments in the followingdescription with reference to the Figures, in which like numbersrepresent the same or similar elements. Reference throughout thisspecification to “one embodiment,” “an embodiment,” or similar languagemeans that a particular feature, structure, or characteristic describedin connection with the embodiment is included in at least one embodimentof the present invention. Thus, appearances of the phrases “in oneembodiment,” “in an embodiment,” and similar language throughout thisspecification may, but do not necessarily, all refer to the sameembodiment.

The described features, structures, or characteristics of the inventionmay be combined in any suitable manner in one or more embodiments. Inthe following description, numerous specific details are recited toprovide a thorough understanding of embodiments of the invention. Oneskilled in the relevant art will recognize, however, that the inventionmay be practiced without one or more of the specific details, or withother methods, components, materials, and so forth. In other instances,well-known structures, materials, or operations are not shown ordescribed in detail to avoid obscuring aspects of the invention.

In certain embodiments, Applicant's pathogen-resistant coating comprisesa polymeric material comprising a plurality of polymer chains. By“pathogen-resistant coating,” Applicant means a coating that renders apathogen non-toxic when that pathogen comes into contact with thecoating. By “pathogen,” Applicant means a toxic chemical, bacterium,virus, protozoa, fungi, parasite, microbe, and combinations thereof.

In certain embodiments, Applicant's pathogen-resistant coating comprisespolyvinyl alcohol (“PVOH”). In certain embodiments, Applicant'spathogen-resistant coating comprises nylon. In certain embodiments,Applicant's pathogen-resistant coating comprises polyvinylchloride. Incertain embodiments, Applicant's pathogen-resistant coating comprisespolyurethane.

In certain embodiments, Applicant's pathogen-resistant coating comprisesan alkyl polysiloxane, such as for example polydimethylsiloxane, orpolysiloxane polymer having fluorinated alkyl groups within itsstructure. In certain embodiments, Applicant's pathogen-resistantcoating is formed using a silicone urethane oligomer sold in commerce bySartomer Company (Exton, Pa.) under the trade name CN 990 siliconizedurethane acrylate. The starting material does not comprise a pureurethane polymer. Rather, this material comprises an oligomer havingreactive acrylate end groups and a midsection having alkyl urethanegroups with polydimethylsiloxane grafted onto the oligomer.

In use, Applicant's pathogen-resistant coating is disposed over one ormore surfaces of a substrate. In the illustrated embodiment of FIG. 1A,composite 100 comprises Applicant's pathogen-resistant coating 110disposed over one surface of substrate 101. As those skilled in the artwill appreciate, pathogen-resistant coating 110 comprises a plurality ofmacromolecules, i.e. polymers. That plurality of individual polymericmolecules in combination form pathogen-resistant coating 110.

Alternatively, pathogen-resistant coating 110 comprises a blend of oneor more polymeric materials. In certain embodiments, pathogen-resistantcoating 110 comprises a blend of PVOH and polyethyleneimine (“PEI”). Incertain embodiments, pathogen-resistant coating 110 comprises a blendhaving PEI/PVOH, wherein the PEI is present in an amount exceeding about60 weight percent. Applicant has found that addition of PVOH to PEIconsiderably enhances the durability of both the primer layer and of thefinal the multi-layer coating, and produces a tougher, more tearresistant multi-layer coating. As those skilled in the art willappreciate, such coatings for shelters are often subjected to abrasionfrom both mechanical forces, i.e. handling, as well as environmentalfactors, i.e. dust, hail, wind, and the like.

In certain embodiments, substrate 101 comprises a fabric. By “fabric,”Applicant means a flexible, planar material formed by weaving or feltingor knitting or crocheting natural and/or synthetic fibers.

In certain embodiments, substrate 101 comprises polyvinylchloride. Incertain embodiments, substrate 101 comprises cotton. In certainembodiments, substrate 101 comprises canvas. In certain embodiments,substrate 101 comprises leather. In certain embodiments, substrate 101comprises polyurethane. In certain embodiments, substrate 101 comprisespolyvinylalcohol.

In certain embodiments, substrate 101 comprises a multi-layer laminate.In the illustrated embodiment of FIG. 1B, substrate 101 comprises afirst polymeric material 103 and a second polymeric material 105. Incertain embodiments, first polymeric material 103 comprisespolyvinylalcohol. In certain embodiments, first polymeric material 103comprises biaxially oriented polyvinylalcohol.

In certain embodiments, second polymeric material 105 comprises athermoplastic material. In certain embodiments, second polymericmaterial 105 comprises a heat-sealable material. In certain embodiments,second polymeric material 105 comprises polypropylene.

In the illustrated embodiment of FIG. 1C, substrate 101 comprises afirst polymeric material 103, second polymeric material 105, and thirdpolymeric material 107. In certain embodiments, third polymeric material107 comprises a thermoplastic material. In certain embodiments, thirdpolymeric material 107 comprises a heat-sealable material. In certainembodiments, third polymeric material 107 comprises polypropylene.

Referring now to FIG. 2, composite 200 comprises a firstpathogen-resistant coating 110 disposed on a first surface of substrate101 and a second pathogen-resistant coating 210 disposed on a secondsurface of substrate 101. In certain embodiments, firstpathogen-resistant coating 110 and second pathogen-resistant coating 210are the same. In certain embodiments, first pathogen-resistant coating110 and second pathogen-resistant coating 210 differ.

Applicant has developed pathogen-resistant coatings that comprise aphotocatalyst that is capable of producing singlet oxygen from ambienttriplet oxygen. The reaction scheme for generation of singlet oxygen isshown below:

Singlet Oxygen Production

photocatalyst+light→¹photocatalyst→³photocatalyst³photocatalyst+³O₂→photocatalyst+¹O₂

In certain embodiments, Applicant's photocatalyst comprises one or morephthalocyanine moieties, such as substituted phthalocyanine 1:

wherein R1 is selected from the group consisting of SO₃H, CO₂H, SO₂Cl,and CHO, and wherein R2 is selected from the group consisting of SO₃H,CO₂H, SO₂Cl, and CHO, and wherein R3 is selected from the groupconsisting of SO₃H, CO₂H, SO₂Cl, and CHO, and wherein R4 is selectedfrom the group consisting of SO₃H, CO₂H, SO₂Cl, and CHO. All of these Pccomplexes exhibit significant absorption in the visible light spectrum(λ_(MAX)≈680 nm) and generate singlet oxygen in high quantum yields atthese wavelengths.

In certain embodiments, one or more of substituents R1, R2, R3, and/orR4 comprise a moiety capable of reversibly reacting with singlet oxygen,as described hereinbelow. In certain embodiments, one or more ofsubstituents R1, R2, R3, and/or R4 comprise a graft moiety which allowsthe phthalocyanine complex to be grafted onto a polymer backbone.

In certain embodiments, Applicant's phthalocyanine does not comprise ametal. In other embodiments, Applicant's phthalocyanine comprises ametal M, wherein M is selected from the group consisting of Zn, Si, Ge,Al, and mixtures thereof,

In certain embodiments, Applicant's photocatalyst comprises one or moresubstituted porphyrin moieties, such as substituted porphyrin 2, whereinR1, R2, R3, and R4, are described hereinabove.

Applicant has developed fillers comprising one or more photocatalystsselected from the group consisting of substituted phthalocyanine (“Pc”)complexes and substituted porphyrin (“P_(OR)”) complexes, wherein thoseone or more photocatalysts become highly photoactive upon exposure tovisible light and generate singlet oxygen from ambient air. Applicant'sphotocatalysts rapidly generate excited singlet state oxygen (typicallywithin a few nanoseconds) after exposure to light. Singlet oxygen hasbeen shown to be a very effective oxidizing agent capable of decomposingboth toxic chemicals as well as pathogens. The high chemical stabilityof these complexes enables them to continually produce singlet oxygenover a long time period without losing their activity. Furthermore,Applicant's photocatalysts are inexpensive, widely available, and are oflow toxicity making them attractive self-regenerating candidatecatalysts for toxic chemical/pathogen deactivation.

In certain embodiments, one or more photocatalysts are directly graftedonto the polymers comprising Applicant's pathogen-resistant coating,and/or added as a filler dispersed within one or more of coatings 110(FIGS. 1A and 2) and/or 210 (FIG. 2). In certain embodiments,Applicant's photocatalysts are used in combination with titanium dioxidenanoparticles which are also photoreactive. In certain embodiments,Applicant's pathogen-resistant coating includes a plurality ofphotocatalysts comprising a first photocatalyst comprising a firststructure and a second photocatalyst comprising a second structure,wherein the first structure differs from the second structure.

In certain embodiments, Applicant's pathogen-resistant coating comprisesone or more photocatalysts, in combination with one or more compoundsthat function as singlet oxygen storage systems, i.e. a reversiblesinglet oxygen trap. As illustrated below, Singlet Oxygen Trap 3reversibly adds singlet oxygen molecule 4 to form endoperoxide 5.

In certain embodiments, Applicant's pathogen-resistant coating comprisesone or more photocatalysts in combination with one or more singletoxygen trap molecules/moieties. In these embodiments, Applicant's one ormore photocatalysts produce singlet oxygen during daylight hours,wherein a portion of that singlet oxygen remains available to oxidizepathogens, and wherein a portion of the singlet oxygen produced isscavenged, i.e. stored, by the one or more singlet oxygen traps whichthen release that stored singlet oxygen throughout the nighttime hoursgiving Applicant's pathogen-resistant coating a time-releasedecontamination capability.

In certain embodiments, Applicant's singlet oxygen trap comprisessubstituted 9,10-diphenylanthracene, compound 6, wherein R9 is H, CH₃,OCH₃, and R10 is H, CH₃, and OCH₃.

9,10-diphenylanthracene reversibly adds singlet oxygen generated byApplicant's photocatalyst to form the 9,10-endoperoxide compound 7.Endoperoxide 7 releases singlet oxygen over time.

In other embodiments, Applicant's singlet oxygen trap comprises3-(4-methyl-1-naphthylpropionic acid. In these embodiments, the3-(4-methyl-1-naphthylpropionic acid reversibly adds singlet oxygenproduced Applicant's one or more photocatalysts to form endoperoxide 8.

Endoperoxide 8 releases singlet oxygen over time.

In other embodiments, Applicant's singlet oxygen trap comprises9,10-diphenylanthracene-2,3-dicarboxylic acid methyl ester. In theseembodiments, the 9,10-diphenylanthracene-2,3-dicarboxylic acid methylester reversibly adds singlet oxygen produced by Applicant's one or morephotocatalysts to form endoperoxide 9.

Endoperoxide 9 releases singlet oxygen over time.

In other embodiments, Applicant's shelter coating includes rubrene,alkyl naphthalenes, stryryl anthracene copolymers, methyl substitutedpoly(vinylnaphthalenes, 2,5-diphenylfuran. As a general matter,1,4-substituted naphthalenes having electron donating substitutents arepreferred scavengers based upon their commercial availability andability to reversibly re-generate singlet oxygen in high yield.

In still other embodiments, Applicant's singlet oxygen trap comprises asubstituted pyridone 10 which reversibly adds singlet oxygen produced byApplicant's one or more photocatalysts to form endoperoxide 11.

In certain embodiments, R5 is selected from the group consisting of Hand CH₃. In certain embodiments, R6 is selected from the groupconsisting of H and CH₃. In certain embodiments, R7 is selected from thegroup consisting of H and CH₃. In certain embodiments, R8 is selectedfrom the group consisting of phenyl, benzyl, p-CN phenyl, (CH₂)₅CH₃,CH₂CO₂CH₃, CH₂CO₂CH₂CH₃, and OH.

In yet other embodiments, Applicant's singlet oxygen trap comprises asubstituted isoquinolinone 12 which reversibly adds singlet oxygenproduced by Applicant's one or more photocatalysts to form endoperoxide13.

In certain embodiments, Applicant's pathogen-resistant coating comprisesa compound dispersed therein, wherein that compound comprises aphotocatalyst moiety and one or more singlet oxygen trap moieties. Forexample and referring now to FIG. 16A, cyanotoluene 1610 is brominatedto form compound 1620 which is oxidized to form aldehyde 1630 which iscyclized to form substituted porphyrin 1640. Referring now to FIG. 16B,substituted porphyrin 1640 is reacted with pyridone anion 1650 to formtetra-pyridone substituted porphyrin 1660. Compound 1660 comprises aporphyrin photocatalyst moiety in combination with four pendent pyridonesinglet oxygen trap moieties.

In certain embodiments, tetra-pyridone substituted porphyrin 1660 isdispersed within Applicant's pathogen-resistant coating 110 and/or 210.Applicant has found that tetra-pyridone substituted porphyrin 1660 isincompatible with the polymers comprising pathogen-resistant coating 110and/or 210, and as a result, tetra-pyridone substituted porphyrin 1660blooms to the surface of that coating.

Referring now to FIG. 14, phthalocyanine complex 1410 is reacted withchlorosulfonic acid 1420 to form substituted phthalocyanine complex 1430which is reacted with substituted pyridone 10 to form tetra-pyridonesubstituted phthalocyanine complex 1450. Compound 1450 comprises aphthalocyanine photocatalyst moiety in combination with four pendentpyridone singlet oxygen traps.

In certain embodiments, tetra-pyridone substituted phthalocyaninecomplex 1450 is dispersed within Applicant's pathogen-resistant coating110 and/or 210. Applicant has found that tetra-pyridone substitutedphthalocyanine complex 1450 is incompatible with the polymers comprisingpathogen-resistant coating 110 and/or 210, and as a result,tetra-pyridone substituted phthalocyanine complex 1450 blooms to thesurface of that coating.

Referring now to FIG. 3A, in certain embodiments Applicant'spathogen-resistant coating comprises polymer 300, wherein polymer 300comprises a plurality of photocatalysts, and a plurality of singletoxygen traps, chemically bonded to thereto. By “chemically bondedthereto,” Applicant means disposed in a pendent group, wherein thatpendent group is attached to a polymer chain. In certain embodiments,polymer 300 comprises for example and without limitation polyvinylalcohol, nylon, polystyrene, polyethylene, polypropylene, cellulose,polyacrylates, polyalkykacrylates, polycarbonate, polyvinylchloride,polyurethane, siloxane, a cellulosic material such as rayon, and thelike, and combinations thereof.

In the illustrated embodiment of FIG. 3A, polymer 300 comprisesphotocatalyst 310 and photocatalyst 330 chemically bonded thereto, incombination with singlet oxygen trap 320 and singlet oxygen trap 340chemically bonded thereto. In certain embodiments, singlet oxygen trap320 comprises a first structure and singlet oxygen trap 340 comprises asecond structure, wherein the first structure differs from the secondstructure. In certain embodiments, photocatalyst 310 comprises a firststructure and photocatalyst 330 comprises a second structure, whereinthe first structure differs from the second structure.

Referring now to FIG. 15A, tetra-chlorosulfonated phthalocyanine complex1510 is reacted with diamine 1515 to form derivatized phthalocyaninecomplex 1520 comprising a plurality of pendent amino groups. Derivatizedphthalocyanine complex 1520 is reacted with cyanuric chloride 1530 toform derivatized phthalocyanine complex 1540 comprising a plurality ofpendent cyanuric chloride groups. Referring now to FIG. 15B, derivatizedphthalocyanine complex 1540 is reacted with a hydroxyl group on polymer300 to form polymer 1500 which comprises a pendent group 1550 comprisingsubstituted Al-phthalocyanine photocatalyst 1552.

Referring now to FIG. 17, tetra-chlorosulfonated photocatalyst 1710 isreacted with an aminosiloxane, such as for example and withoutlimitation gamma-aminopropyltrialkoxysilane 1720 to formtetrasiloxy-substituted photocatalyst 1730. In certain embodiments, thetetra-chlorosulfonated photocatalyst 1710 comprises a substitutedphthalocyanine. In certain embodiments, the tetra-chlorosulfonatedphotocatalyst 1710 comprises a substituted porphyrin. In certainembodiments, gamma-aminopropyltrialkoxysilane 1720 comprisesgamma-aminopropyltrimethoxysilane. In certain embodiments,gamma-aminopropyltrialkoxysilane 1720 comprisesgamma-aminopropyltriethoxysilane. Tetrasiloxy-substituted photocatalyst1730 is reacted with hydroxy-substituted polymer 300 to form polymer1700 which comprises a pendent group 1740 comprising a photocatalystselected from the group consisting of a substituted phthalocyanine and asubstituted porphyrin.

In certain embodiments, Applicant's pathogen-resistant coating comprisesa plurality of polymers 1700 in combination with a plurality of singletoxygen traps 1450. In certain embodiments, Applicant'spathogen-resistant coating comprises a plurality of polymers 1700 incombination with a plurality of singlet oxygen traps 1660.

Referring now to FIG. 3B, in certain embodiments pathogen-resistantcoating 305 comprises a plurality of polymers 300 which in combinationform pathogen-resistant coating 305. In certain embodiments, Applicant'spathogen-resistant coating 305 comprises a first plurality of polymers300 and a second plurality of polymers 300, wherein each of the firstplurality of polymers 300 comprise a photocatalyst 310 and each of thesecond plurality of polymers 300 comprise a photocatalyst 330. Incertain embodiments, Applicant's pathogen-resistant coating 305comprises a first plurality of polymers 300 and a second plurality ofpolymers 300, wherein each of the first plurality of polymers 300comprise a singlet oxygen trap 320, and each of the second plurality ofpolymers 300 comprise a singlet oxygen trap 340.

FIG. 4 illustrates pathogen-resistant coating 305A disposed on a firstsurface of substrate 101. In certain embodiments, Applicant'spathogen-resistant coating 305A comprises a first plurality of polymers300 and a second plurality of polymers 300, wherein each of the firstplurality of polymers 300 comprise a photocatalyst 310 and each of thesecond plurality of polymers 300 comprise a photocatalyst 330. Incertain embodiments, Applicant's pathogen-resistant coating 305Acomprises a first plurality of polymers 300 and a second plurality ofpolymers 300, wherein each of the first plurality of polymers 300comprise a singlet oxygen trap 320, and each of the second plurality ofpolymers 300 comprise a singlet oxygen trap 340.

FIG. 5 illustrates pathogen-resistant coating 305A disposed on a firstsurface of substrate 101, and pathogen-resistant coating 305B disposedon a second surface of substrate 101. In certain embodiments,Applicant's pathogen-resistant coating 305B comprises a first pluralityof polymers 300 and a second plurality of polymers 300, wherein each ofthe first plurality of polymers 300 comprise a photocatalyst 520 andeach of the second plurality of polymers 300 comprise a photocatalyst540. In certain embodiments, Applicant's pathogen-resistant coating 305Bcomprises a first plurality of polymers 300 and a second plurality ofpolymers 300, wherein each of the first plurality of polymers 300comprise a singlet oxygen trap 510, and each of the second plurality ofpolymers 300 comprise a singlet oxygen trap 530.

Referring now to FIG. 6A, in certain embodiments Applicant'spathogen-resistant coating comprises polymer 600, wherein polymer 600comprises a plurality of photocatalysts chemically bonded to thereto incombination with a plurality of singlet oxygen traps chemically bondedthereto. In certain embodiments, polymer 600 comprises polyvinylalcohol, nylon, polyvinylchloride, polyurethane, siloxane, a cellulosicmaterial such as rayon, and the like, and combinations thereof.

In the illustrated embodiment of FIG. 6A, polymer 600 comprisesphotocatalysts 610, 620, 630, and 640 chemically bonded thereto. Furtherin the illustrated embodiment of FIG. 6A, singlet oxygen trap 650 ischemically bonded to photocatalyst 610, singlet oxygen trap 660 ischemically bonded to photocatalyst 630, singlet oxygen trap 670 ischemically bonded to photocatalyst 630, and singlet oxygen trap 680 ischemically bonded to photocatalyst 640.

Referring now to FIG. 12A, tetra-substituted porphyrin 1210 is reactedwith 2 equivalents of pyridone 10 to form di-pyridone substitutedporphyrin 1220 which is reacted with diamine 1230 and then with cyanuricchloride 1240 to form di-pyridone, di-cyanuric chloride substitutedporphyrin 1250. Referring now to FIG. 12B, di-pyridone, di-cyanuricchloride substituted porphyrin 1250 is reacted with a hydroxyl group onpolymer 600 to form polymer 1200 comprising polymeric backbone 600having pendent group 1260 attached thereto. Pendent group 1260 comprisesporphyrin photocatalyst 1266 in combination with pyridone singlet oxygentrap 1262 and pyridone oxygen trap 1264.

As those skilled in the art will appreciate, adjusting the equivalentsof pyridone 10, diamine 1230, and cyanuric chloride 1240 used, thereaction scheme of FIGS. 12A and 12B can be modified to form a polymer600 comprising a pendent group which comprises porphyrin photocatalyst1266 in combination with one, two, or three, pyridone singlet oxygentraps 1262.

Referring now to FIG. 13A, tetra-substituted phthalocyanine 1310 isreacted with 2 equivalents of pyridone 10 to form di-pyridonesubstituted phthalocyanine 1320 which is reacted with diamine 1330 andthen with cyanuric chloride 1340 to form di-pyridone, di-cyanuricchloride substituted phthalocyanine 1350. Referring now to FIG. 13B,di-pyridone, di-cyanuric chloride substituted phthalocyanine 1350 isreacted with a hydroxyl group on polymer 600 to form polymer 1300comprising polymeric backbone 600 having pendent group 1360 attachedthereto. Pendent group 1360 comprises phthalocyanine photocatalyst 1366in combination with pyridone singlet oxygen trap 1362 and pyridoneoxygen trap 1364.

As those skilled in the art will appreciate, adjusting the equivalentsof pyridone 10, diamine 1330, and cyanuric chloride 1340 used, thereaction scheme of FIGS. 13A and 13B can be modified to form a polymer600 comprising a pendent group which comprises phthalocyaninephotocatalyst 1366 in combination with one, two, or three, pyridonesinglet oxygen traps 1362.

Referring now to FIG. 18, tetra-chlorosulfonated photocatalyst 1810 isreacted with 2 equivalents of gamma-aminopropyltrialkoxysilane 1820 and2 equivalents of amino-substituted pyridone 10 to formdi-siloxy-di-pyridone-substituted photocatalyst 1830. In certainembodiments, di-siloxy-di-pyridone-substituted photocatalyst 1830comprises a substituted phthalocyanine. In certain embodiments,di-siloxy-di-pyridone-substituted photocatalyst 1830 comprises asubstituted porphyrin. In certain embodiments,gamma-aminopropyltrialkoxysilane 1820 comprisesgamma-aminopropyltrimethoxysilane. In certain embodiments,gamma-aminopropyltrialkoxysilane 1820 comprisesgamma-aminopropyltriethoxysilane. Di-siloxy-di-pyridone-substitutedphotocatalyst 1830 is reacted with polymer 300 to form polymer 1800which comprises a pendent group 1840 comprising a photocatalyst selectedfrom the group consisting of a substituted phthalocyanine and asubstituted porphyrin in combination with singlet oxygen trap pyridone1860 and singlet oxygen trap pyridone 1870.

As those skilled in the art will appreciate, adjusting the equivalentsof pyridone 10, and amino-siloxane 1820 used, the reaction scheme ofFIG. 18 can be modified to form a polymer 1800 comprising a pendentgroup which comprises photocatalyst 1850 in combination with a onepyridone singlet oxygen trap or with three pyridone singlet oxygentraps.

Referring now to FIG. 6B, in certain embodiments pathogen-resistantcoating 605 comprises a plurality of polymers 600. In certainembodiments, Applicant's pathogen-resistant coating 605 comprises afirst plurality of polymers 600 and a second plurality of polymers 600,wherein each of the first plurality of polymers 600 comprise aphotocatalyst 610 in combination with a singlet oxygen trap 650, andeach of the second plurality of polymers 600 comprise a photocatalyst620 in combination with a singlet oxygen trap 660. In certainembodiments, Applicant's pathogen-resistant coating 605 furthercomprises a third plurality of polymers 600 and a fourth plurality ofpolymers 600, wherein each of the third plurality of polymers 600comprise a photocatalyst 630 in combination with a singlet oxygen trap670, and each of the fourth plurality of polymers 600 comprise aphotocatalyst 640 in combination with a singlet oxygen trap 680.

FIG. 7 illustrates pathogen-resistant coating 605A disposed on a firstsurface of substrate 101. In certain embodiments, Applicant'spathogen-resistant coating 605A comprises a first plurality of polymers600 and a second plurality of polymers 600, wherein each of the firstplurality of polymers 600 comprise a photocatalyst 610 in combinationwith a singlet oxygen trap 650, and each of the second plurality ofpolymers 600 comprise a photocatalyst 620 in combination with a singletoxygen trap 660. In certain embodiments, Applicant's pathogen-resistantcoating 605A further comprises a third plurality of polymers 600 and afourth plurality of polymers 600, wherein each of the third plurality ofpolymers 600 comprise a photocatalyst 630 in combination with a singletoxygen trap 670, and each of the fourth plurality of polymers 600comprise a photocatalyst 640 in combination with a singlet oxygen trap680.

FIG. 8 illustrates pathogen-resistant coating 605A disposed on a firstsurface of substrate 101, and pathogen-resistant coating 605B disposedon a second surface of substrate 101. In certain embodiments,Applicant's pathogen-resistant coating 605A comprises a first pluralityof polymers 600 and a second plurality of polymers 600, wherein each ofthe first plurality of polymers 600 comprise a photocatalyst 610 incombination with a singlet oxygen trap 650, and each of the secondplurality of polymers 600 comprise a photocatalyst 620 in combinationwith a singlet oxygen trap 660. In certain embodiments, Applicant'spathogen-resistant coating 605A further comprises a third plurality ofpolymers 600 and a fourth plurality of polymers 600, wherein each of thethird plurality of polymers 600 comprise a photocatalyst 630 incombination with a singlet oxygen trap 670, and each of the fourthplurality of polymers 600 comprise a photocatalyst 640 in combinationwith a singlet oxygen trap 680.

In certain embodiments, Applicant's pathogen-resistant coating 605Bcomprises a first plurality of polymers 600 and a second plurality ofpolymers 600, wherein each of the first plurality of polymers 600comprise a photocatalyst 810 in combination with a singlet oxygen trap820, and each of the second plurality of polymers 600 comprise aphotocatalyst 830 in combination with a singlet oxygen trap 840. Incertain embodiments, Applicant's pathogen-resistant coating 605B furthercomprises a third plurality of polymers 600 and a fourth plurality ofpolymers 600, wherein each of the third plurality of polymers 600comprise a photocatalyst 850 in combination with a singlet oxygen trap860, and each of the fourth plurality of polymers 600 comprise aphotocatalyst 870 in combination with a singlet oxygen trap 880.

Referring now to FIG. 9A, in certain embodiments Applicant'spathogen-resistant coating comprises polymer 900, wherein polymer 900comprises a plurality of photocatalysts chemically bonded to thereto incombination with a plurality of singlet oxygen traps chemically bondedthereto. In certain embodiments, polymer 900 comprises polyvinylalcohol, nylon, polyvinylchloride, polyurethane, siloxane, a cellulosicmaterial such as rayon, and the like, and combinations thereof.

In the illustrated embodiment of FIG. 9A, polymer 900 comprisesphotocatalysts 910 and 940 chemically bonded thereto. Further in theillustrated embodiment of FIG. 9A, singlet oxygen traps 920 and 930 aredisposed in pendent groups attached to photocatalyst 910, and singletoxygen traps 950 and 960 are disposed in pendent groups attached tophotocatalyst 940.

Referring now to FIG. 9B, in certain embodiments pathogen-resistantcoating 905 comprises a plurality of polymers 900. In certainembodiments, Applicant's pathogen-resistant coating 905 comprises afirst plurality of polymers 900 and a second plurality of polymers 900,wherein each of the first plurality of polymers 900 comprise aphotocatalyst 910 in combination with singlet oxygen traps 920 and 930,and each of the second plurality of polymers 900 comprise aphotocatalyst 940 in combination with singlet oxygen traps 950 and 960.

FIG. 10 illustrates pathogen-resistant coating 905A disposed on a firstsurface of substrate 101. In certain embodiments, Applicant'spathogen-resistant coating 905A comprises a first plurality of polymers900 and a second plurality of polymers 900, wherein each of the firstplurality of polymers 900 comprise a photocatalyst 910 in combinationwith singlet oxygen traps 920 and 930, and each of the second pluralityof polymers 900 comprise a photocatalyst 940 in combination with singletoxygen traps 950 and 960.

FIG. 11 illustrates pathogen-resistant coating 905A disposed on a firstsurface of substrate 101, and pathogen-resistant coating 905B disposedon a second surface of substrate 101. In certain embodiments,Applicant's pathogen-resistant coating 905A comprises a first pluralityof polymers 900 and a second plurality of polymers 900, wherein each ofthe first plurality of polymers 900 comprise a photocatalyst 910 incombination with singlet oxygen traps 920 and 930, and each of thesecond plurality of polymers 900 comprise a photocatalyst 940 incombination with singlet oxygen traps 950 and 960. In certainembodiments, Applicant's pathogen-resistant coating 905B comprises afirst plurality of polymers 900 and a second plurality of polymers 900,wherein each of the first plurality of polymers 900 comprise aphotocatalyst 1110 in combination with singlet oxygen traps 1120 and1130, and each of the second plurality of polymers 900 comprise aphotocatalyst 1140 in combination with singlet oxygen traps 1150 and1160.

While the preferred embodiments of the present invention have beenillustrated in detail, it should be apparent that modifications andadaptations to those embodiments may occur to one skilled in the artwithout departing from the scope of the present invention as set forthin the following claims.

1. A pathogen-resistant fabric, comprising: a plurality of polyurethanepolymer chains; a phthalocyanine photocatalyst chemically bonded to saidplurality of polyurethane polymer chains; and a singlet oxygen trapmolecule chemically bonded to said photocatalyst, wherein said singletoxygen trap reacts with singlet oxygen produced by said photocatalyst.2. The pathogen-resistant fabric of claim 1, further comprising: twosinglet oxygen trap molecules chemically bonded to said photocatalyst,wherein said two or more oxygen trap molecules react with singlet oxygenproduced by said photocatalyst.
 3. The pathogen-resistant fabric ofclaim 2, wherein: said two singlet oxygen trap molecules comprise afirst singlet oxygen trap molecule comprising a first structure and asecond singlet oxygen trap molecule comprising a second structure; andsaid first structure differs from said second structure.
 4. Thepathogen-resistant fabric of claim 1, further comprising: four oxygentrap molecules chemically bonded to said photocatalyst, wherein saidfour oxygen trap molecules react with singlet oxygen produced by saidphotocatalyst.
 5. A pathogen-resistant fabric, comprising: a pluralityof polyurethane polymer chains; a phthalocyanine photocatalystchemically bonded to said plurality of polyurethane polymer chains; anda singlet oxygen trap molecule chemically bonded to said plurality ofpolyurethane polymer chains, wherein said singlet oxygen trap reactswith singlet oxygen produced by said photocatalyst.